1,2-Dimethoxyethane → Ethyl 4-amino-3,6-dimethyl-2-(3-pyridinyl)thieno[2,3-b]pyridine-5-carboxylate

HRID 573557Notes

Reaction equation

[NH2:1][C:2]1[C:7]([C:8]([O:10][CH2:11][CH3:12])=[O:9])=[C:6]([CH3:13])[N:5]=[C:4]2[S:14][C:15](Br)=[C:16]([CH3:17])[C:3]=12.C(=O)([O-])[O-].[Na+].[Na+].[N:25]1[CH:30]=[CH:29][CH:28]=[C:27](B(O)O)[CH:26]=1.COCCOC>C(#N)C.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[NH2:1][C:2]1[C:7]([C:8]([O:10][CH2:11][CH3:12])=[O:9])=[C:6]([CH3:13])[N:5]=[C:4]2[S:14][C:15]([C:27]3[CH:26]=[N:25][CH:30]=[CH:29][CH:28]=3)=[C:16]([CH3:17])[C:3]=12

Participants

Conditions

Temperature: 70 °C

Procedure

A mixture of ethyl 4-amino-2-bromo-3,6-dimethylthieno[2,3-b]pyridine-5-carboxylate (260 mg, 0.790 mmol) (Description 31), tetrakis(triphenylphosphine)palladium(0) (45.6 mg, 0.039 mmol), sodium carbonate (167 mg, 1.580 mmol) and 3-pyridineboronic acid (116 mg, 0.948 mmol) in acetonitrile (3 mL) and water (0.75 μl) was heated at 70° C. under nitrogen, for 30 min. 1,2-Dimethoxyethane (2 mL) was added and the mixture was stirred at 80° C. for 18 h. The reaction mixture was cooled to RT and concentrated. Purification by chromatography on silica gel, eluting with a gradient of 0-50% ethyl acetate in DCM, afforded the title compound (141 mg). LCMS (A) m/z: 328 [M+1]+, Rt 0.88 min (acidic), Rt 1.14 min (basic).

Workup

temperatureThe reaction mixture was cooled to RT
concentrationconcentrated
customPurification by chromatography on silica gel
washeluting with a gradient of 0-50% ethyl acetate in DCM

Sources & evidence

ORD record: ord-c3f2dc5a49414478bf0c336086850d21
Source dataset: uspto-grants-2015_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09029545B2

Reaction notes

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